CN109694465B - Thiophene copolymer and preparation method and application thereof - Google Patents
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229920001577 copolymer Polymers 0.000 title claims abstract description 92
- 229930192474 thiophene Natural products 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000007772 electrode material Substances 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 229940126062 Compound A Drugs 0.000 claims description 17
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 18
- 229920000642 polymer Polymers 0.000 abstract description 16
- 239000007787 solid Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 9
- 150000001335 aliphatic alkanes Chemical group 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 239000003990 capacitor Substances 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000011889 copper foil Substances 0.000 description 12
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001623 magnesium bromide Inorganic materials 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 3
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- -1 Polytetrafluoroethylene Polymers 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- LJCQJWFOVZOCLH-UHFFFAOYSA-L magnesium butane dibromide Chemical compound [Br-].[Mg+2].CCCC.[Br-] LJCQJWFOVZOCLH-UHFFFAOYSA-L 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KPOCSQCZXMATFR-UHFFFAOYSA-N 3-butylthiophene Chemical compound CCCCC=1C=CSC=1 KPOCSQCZXMATFR-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HERSKCAGZCXYMC-UHFFFAOYSA-N thiophen-3-ol Chemical group OC=1C=CSC=1 HERSKCAGZCXYMC-UHFFFAOYSA-N 0.000 description 2
- LRLQQERNMXHASR-UHFFFAOYSA-N 2-diphenylphosphanylpropan-2-yl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 LRLQQERNMXHASR-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBQUMMFUJLOTQC-UHFFFAOYSA-N dichloronickel;3-diphenylphosphaniumylpropyl(diphenyl)phosphanium Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1[PH+](C=1C=CC=CC=1)CCC[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical class CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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Abstract
The invention relates to a thiophene copolymer and a preparation method and application thereof. The thiophene copolymer has the following structural formula:
wherein, x: y is 10: 1-30: 1 and n is an integer of 1-20. The thiophene copolymer contains long-chain alkane groups and hydroxyl groups. The long-chain alkane group enables the thiophene copolymer to have the viscous liquid property, and the hydroxyl group can generate curing reaction with the curing agent so as to form a solid state. The thiophene copolymer with the structure has good adhesive property, and the cured polymer has good conductivity.
Description
Technical Field
The invention relates to the technical field of new high-molecular materials, in particular to a thiophene copolymer and a preparation method and application thereof.
Background
The super capacitor is a novel energy storage device and has the advantages of high power density, long cycle life and the like. The performance of the super capacitor is greatly related to the manufacturing process of the pole piece, such as the type of the binder, the proportion of the binder during mixing, and the like. Currently, polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), and Styrene Butadiene Rubber (SBR) are commonly used as binders. Wherein PVDF is easy to swell, PTFE has poor dispersibility, and CMC and SBR are easy to decompose. In view of the characteristics of all current binders, since the binders are non-conductive, the overall electron transport and conductivity properties of the electrode materials are reduced in use, and a certain proportion of conductive materials is generally required to be added.
Therefore, the development of a material with good adhesive property and conductivity is urgently needed, so that the conductivity of the supercapacitor can be improved, and the preparation cost of the electrode material can be reduced.
Disclosure of Invention
Based on this, there is a need for thiophene copolymers with both good adhesion properties and electrical conductivity, and methods of making and using the same.
A thiophene copolymer having the formula:
wherein, x: y is 10: 1-30: 1 and n is an integer of 1-20.
In one embodiment, x: y is 25: 1-30: 1.
in one embodiment, -CnH2n+1Is straight chain alkyl.
In one embodiment, n is an integer from 12 to 16.
A preparation method of thiophene copolymer comprises the following steps:
providing a compound A and a compound B, wherein the structural formulas of the compound A and the compound B are as follows:
A:
B:
wherein n is an integer of 1-20; and
mixing a compound A and a compound B according to a molar ratio of x: y, and reacting in the presence of a solvent and a catalyst to obtain the thiophene copolymer, wherein the thiophene copolymer has a structural formula as follows:
wherein n is an integer of 1-20, x: y is 10: 1-30: 1.
in one embodiment, the molar ratio of compound a to compound B, x: y is 25: 1-30: 1, the solvent is CHCl3The catalyst is FeCl3And the ratio of the number of moles of the catalyst to the sum of the number of moles of the compound A and the compound B is 0.5 to 1:10 to 20.
In one embodiment, -CnH2n+1Is straight chain alkyl.
In one embodiment, n is an integer from 12 to 16.
Use of a thiophene copolymer according to any of the preceding claims or a thiophene copolymer prepared by a method for preparing a thiophene copolymer according to any of the preceding claims in a binder.
An electrode active material comprises a thiophene copolymer, a carbon material and a curing agent, wherein the mass ratio of the thiophene copolymer to the carbon material to the curing agent is 70-95: 4.5-30: 0.01-0.5, wherein the thiophene copolymer has the following structural formula:
wherein, x: y is 10: 1-30: 1 and n is an integer of 1-20.
The thiophene copolymer contains long-chain alkane groups and hydroxyl groups, wherein the molar ratio x of thiophene units containing long-chain alkane groups to thiophene units containing hydroxyl groups is as follows: y is 10: 1-30: 1. the long-chain alkane group enables the thiophene copolymer to have the viscous liquid property, and the hydroxyl group can generate curing reaction with the curing agent so as to form a solid state. The thiophene copolymer with the structure has good adhesive property, and the cured polymer has good conductivity.
When the thiophene copolymer is used for preparing the super capacitor, the thiophene copolymer can be directly used as a binder, a solvent is not needed, a conductive agent is not needed to be additionally added into an electrode material, the capacitor has higher specific capacitance, and the preparation cost of the electrode material is reduced.
Drawings
Fig. 1 is a flowchart of a method for producing a thiophene copolymer according to an embodiment.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
One embodiment of a thiophene copolymer has the following structural formula:
wherein, x: y is 10: 1-30: 1 and n is an integer of 1-20.
Specifically, the composition ratio of y has a great influence on the structure of the polymer after the post-curing reaction, and the larger y is, the higher the amount of the curing agent is relatively, and the lower the conductivity of the cured polymer is. However, too small a y-ratio results in slow curing reactions, and the polymer remains liquid after curing or degrades over time in the solid state. In the present embodiment, x: y may be 10: 1-30: 1, such as 10: 1. 15:1, 20:1, 25:1, 30:1, etc. Preferably, x: y is 25: 1-30: 1, the thiophene copolymer is liquid at normal temperature, has good viscosity and higher melting point after being solidified, and can be directly used as a binder of an electrode material at normal temperature. Particularly preferably, x: y is 25: 1.
preferably, the value range of x is 100-200, and the value range of y is 5-10.
Of course, it is understood that when the thiophene copolymer is in a solid state at normal temperature, the thiophene copolymer may be converted into a liquid state by heat treatment or other means, and thus used as a binder for an electrode material.
In particular, -CnH2n+1In the case of a straight-chain alkyl group, the vacancy of the straight-chain alkyl group is relatively small, and the yield at the time of polymerization is high as compared with that of a p-chain alkyl group.
Specifically, n can be any integer from 1 to 20, for example, n is 4, 6, 8, 12 or 16.
Preferably, n is an integer from 12 to 16, for example n is 12, 13, 14, 15 or 16. The more the number of carbon atoms, the better the flexibility of the thiophene copolymer, but the conductivity gradually decreases, thereby affecting the performance of the capacitor.
Particularly preferably, n is 12, while satisfying the flexible liquid state and electrical conductivity of the polymer.
Specifically, the thiophene copolymer is linear and liquid at normal temperature, the copolymer provides-OH groups, and a curing agent containing-N ═ C ═ O groups is added to the copolymer to form a network polymer after curing, so that the network polymer is formed into a solid state.
The thiophene copolymer contains long-chain alkane (-C)nH2n+1) And a hydroxyl group (-OH), the molar ratio x of thiophene units containing a long-chain alkane group to thiophene units containing a hydroxyl group: y is 10: 1-30: 1. the thiophene copolymer has the viscous liquid property due to the long-chain alkane group, and the hydroxyl group can generate curing reaction with the curing agent to form a solid state, so that the thiophene copolymer with the structure has good adhesive property, and the conductivity of the cured polymer is good.
When the thiophene copolymer is used for preparing the super capacitor, the thiophene copolymer can be directly used as a binder, a solvent is not needed, a conductive agent is not needed to be additionally added into an electrode material, the capacitor has higher specific capacitance, and the preparation cost of the electrode material is reduced.
The thiophene copolymer has viscosity, is solid or liquid at normal temperature, and has viscosity suitable for coating processing by directly mixing with a main electrode material.
The preparation method of the thiophene copolymer shown in figure 1 comprises the following steps:
s10, providing compound A and compound B.
The structural formulas of compound a and compound B are as follows:
A：
B：
wherein n is an integer of 1-20.
Specifically, compound a can be prepared by the following steps: dissolving 3-bromothiophene and bis-diphenylphosphinopropane nickel dichloride compound in tetrahydrofuranPyran, slowly adding C after stirring in ice bathnH2n+1MgBr (magnesium bromide alkyl), fully reacting under stirring, and separating and purifying to obtain the compound A. Wherein, 3-bromothiophene, bis diphenylphosphinopropane nickel dichloride compound and CnH2n+1-molar ratio of MgBr of 100: 1: 120.
the preparation process of compound a is shown by the following chemical equation:
the operation of separating and purifying to obtain the compound A comprises the following steps: neutralizing the reaction solution with hydrochloric acid, separating out an organic layer, evaporating the solvent to obtain a crude product, and recrystallizing the crude product in methanol to obtain the compound A.
Preferably, -CnH2n+1The alkyl group is a straight-chain alkyl group, and n is an integer of 12-16.
Specifically, the compound B is 3-hydroxythiophene with the structural formula
Commercially available products.
S20, mixing the compound A and the compound B according to the molar ratio of x: y, and reacting in the presence of a solvent and a catalyst to obtain the thiophene copolymer.
The thiophene copolymer has the following structural formula: thiophene copolymer:
wherein n is an integer of 1-20, x: y is 10: 1-30: 1.
specifically, x: y may be 10: 1-30: 1, such as 10: 1. 15:1, 20:1, 25:1, 30:1, etc.
Preferably, x: y is 25: 1-30: 1, the thiophene copolymer prepared by the proportion is liquid at normal temperature, has good viscosity and higher melting point after solidification, and can be directly used as a binder of an electrode material at normal temperature. Particularly preferably, x: y is 25: 1.
in this embodiment, the solvent is CHCl3. Of course, in other embodiments, the solvent may also be dichloromethane or the like.
In this embodiment, the catalyst is FeCl3。
Specifically, the ratio of the number of moles of the catalyst to the sum of the number of moles of the compound A and the compound B is 0.5 to 1:10 to 20. For example 1: 10.
Specifically, compound a and compound B are reacted at room temperature. The room temperature may be, for example, 0 ℃ to 40 ℃, preferably 25 ℃.
Specifically, the method also comprises the following steps of separating and purifying the obtained thiophene copolymer, wherein the operation of separating and purifying the thiophene copolymer comprises the following steps: and (3) evaporating the solvent from the reaction solution to obtain a crude product, wherein the volume ratio of the crude product to the solvent is 5:1, washing with a mixed solution of methanol and water to obtain the thiophene copolymer.
The preparation method of the thiophene copolymer has the advantages of simple preparation process and non-harsh conditions, and the prepared thiophene copolymer has the advantages of convenient electrode preparation and high specific capacity of electrode materials when being applied to the preparation of capacitors.
The thiophene polymer prepared by the preparation method of the thiophene copolymer has viscosity, is solid or liquid at normal temperature, and has viscosity suitable for being directly mixed with a main electrode material for coating processing.
The thiophene copolymer or the thiophene copolymer prepared by the preparation method of the thiophene copolymer is applied to the binder.
The thiophene copolymer contains-OH groups, and is solidified by adding a curing agent containing-N ═ C ═ O groups to form a network polymer, so that the network polymer forms a solid state, can be directly used as a binder of a capacitor electrode, and greatly simplifies the process for preparing the capacitor electrode.
The electrode active material of an embodiment comprises a thiophene copolymer, a carbon material and a curing agent, wherein the mass ratio of the thiophene copolymer, the carbon material and the curing agent is 70-95: 4.5-30: 0.01-0.5, wherein the thiophene copolymer has the following structural formula:
wherein, x: y is 10: 1-30: 1 and n is an integer of 1-20.
Specifically, -CnH2n+1Is a straight-chain alkyl group, and preferably, n is an integer of 12-16.
Preferably, x: y is 25: 1-30: 1, particularly preferably, x: y is 25: 1.
the specific structure and properties of the thiophene copolymer can be found in the above description, and are not described in detail herein.
Specifically, the carbon material may be selected from at least one of activated carbon, carbon nanotubes, and graphene.
Specifically, the curing agent may be 1, 6-hexamethylene diisocyanate (HDI, chemical formula O ═ C ═ N — CH)2CH2CH2CH2CH2CH2-N＝C＝O)。
According to the electrode active material, the thiophene copolymer generates a curing reaction with the curing agent through the hydroxyl group, so that a solid state is formed, the active material of the electrode formed by the thiophene copolymer, the carbon material and the curing agent has good bonding performance, and the electrical conductivity of the cured polymer is good.
When the electrode active material is used, the electrode active material is directly coated on a current collector to form an electrode plate of the super capacitor. The thiophene copolymer can be directly used as a binder, a solvent is not needed, a conductive agent is not needed to be additionally added into an electrode material, the capacitor has higher specific capacitance, and the preparation cost of the electrode material is reduced.
The electrode active material can be directly coated, and the specific capacitance of the prepared super capacitor can be improved by more than 20% compared with the specific capacitance of the prepared super capacitor using a common binder.
The following are specific examples.
Example 1
The method comprises the following steps: 3-bromothiophene (0.2mol) and NiCl2(dppp)](2mmol) in 200mL THF, ice-bath stirring for one hour, magnesium bromide (0.25mol) slowly added to the mixture, stirring reaction for 12 hours, then 1molNeutralizing with/L hydrochloric acid, separating an organic layer, evaporating the solvent to obtain a crude product, and then recrystallizing in methanol to obtain the 3-butylthiophene monomer (compound A).
Step two: 3-Butylthiophene monomer (0.05mol) was dissolved in 80mLCHCl3In (1), 0.08moL of FeCl is added3And stirring and reacting for 24 hours at room temperature, evaporating the solvent to obtain a crude product, and cleaning by using a methanol/water mixed solution to obtain the polymer of the compound A.
Examples 2 to 5
The method of the steps in the embodiments 2-5 is basically the same as that in the embodiment 1, and the difference is that: example 2 step one magnesium bromide was used instead of magnesium bromide butane in example 1; example 3 in step one, magnesium bromide substituted octane was used instead of magnesium bromide butane in example 1; example 4 in step one, magnesion-dodecane bromide was used instead of magnesiobutane bromide in example 1; example 5 in step one, magnesium bromide was used instead of magnesium bromide butane in example 1. The properties of the thiophene polymers prepared in examples 1-5 are shown in Table 1.
Table 1: melting Point and State at ordinary temperature of Polymer obtained in examples 1 to 5
As can be seen from Table 1, as the number of side chain carbon atoms increases, the melting point of the polymer becomes smaller, and the state of the polymer at room temperature changes from solid to liquid. The magnesiumbromide n-dodecane used in example 4 is preferably selected from the viewpoint that the polymer remains liquid at ordinary temperature and has a melting point, i.e., n is 12.
Examples 6 to 10
Examples 6 to 10 the procedure was substantially the same as in example 4, except that in the second step, 3-hydroxythiophene was added in a certain ratio. Example 6 a: B ═ 10: 1; example 7 a: B ═ 15: 1; example 8 a: B ═ 20: 1; example 9 a: B ═ 25: 1; in example 10, a: B equals 30: 1. And reacting to obtain the thiophene copolymer.
Thiophene copolymer obtained in examples 6 to 10 and 1, 6-hexamethylene diisocyanate (HDI, chemical formula O ═ C ═ N-CH)2CH2CH2CH2CH2CH2The mixing and curing reaction was carried out in the proportions calculated (molar content of-OH in the copolymer is equal to the molar content of-C ═ N ═ O in the HDI). The viscosity and melting point of the copolymer after curing are shown in Table 2.
Table 2: properties of thiophene copolymer obtained in examples 6 to 10
| Examples | State before curing | Viscosity Pa.s | Melting Point after curing (. degree. C.) |
| Example 6 | Dark blue solid | - | 245 |
| Example 7 | Dark blue viscous liquid | 5200 | 214 |
| Example 8 | Deep blue viscousLiquid, method for producing the same and use thereof | 1200 | 205 |
| Example 9 | Blue viscous liquid | 356 | 201 |
| Example 10 | Blue viscous liquid | 215 | 178 |
As can be seen from Table 2, the higher the ratio of x to y, the more the copolymer changes from a solid state to a liquid state, the viscosity of the liquid state becomes smaller as the ratio of y becomes smaller, and the melting point of the cured polymer becomes smaller as the ratio of y becomes smaller. In consideration of the actual mixed coating process and stability, x: y is 25: 1.
Example 11
A copolymer binder for a super capacitor is disclosed, and the method for preparing the electrode for the super capacitor comprises the following steps:
according to the mass ratio of 95: 4.95: the activated carbon, the thiophene copolymer prepared in example 9, and the curing agent were weighed at a ratio of 0.05 and sufficiently stirred to form a uniform black slurry. Wherein 1, 6-Hexamethylene Diisocyanate (HDI) is used as the curing agent, and the chemical formula is O ═ C ═ N-CH2CH2CH2CH2CH2CH2-N ═ C ═ O. The slurry was then uniformly coated on a copper foil. And (3) putting the coated copper foil into a vacuum drying oven to be dried for 2 hours at the temperature of 80 ℃ until the copper foil is completely dried, so as to obtain the electrode for the super capacitor.
Examples 12 to 15
The procedure of examples 12 to 15 was the same as in example 11, except that: activated carbon in example 12: the mass ratio of the thiophene copolymer to the curing agent is 90: 9.9: 0.1. activated carbon in example 13: the mass ratio of the thiophene copolymer to the curing agent is 85: 14.85: 0.15; activated carbon in example 14: the mass ratio of the thiophene copolymer to the curing agent is 80:19.8: 0.2; activated carbon in example 15: the mass ratio of the thiophene copolymer to the curing agent is 70: 29.7:0.3.
Evaluation method of electrode adhesion:
the electrode surfaces prepared in examples 11 to 15 were each cut with a knife at 2mm intervals in the longitudinal and transverse directions to 5 cuts reaching the current collector, and the cut portions were immediately peeled off with tape to visually check the degree of exfoliation of the active material. The test results are shown in table 3.
Table 3: electrode performance testing
| Adhesion Property | Electrode surface | Specific capacitance (F/g) | |
| Example 11 | No peeling occurred | Without cracks | 178 |
| Example 12 | No peeling occurred | Without cracks | 165 |
| Example 13 | No peeling occurred | Without cracks | 158 |
| Example 14 | No peeling occurred | Without cracks | 143 |
| Example 15 | No peeling occurred | Without cracks | 123 |
As can be seen from the data in table 3, the electrode using the thiophene copolymer as the binder exhibited good adhesion, since the active material was not easily detached. With the reduction of the copolymer content, the specific capacitance of the prepared supercapacitor tends to be reduced.
Comparative example 1
Respectively weighing the activated carbon, the conductive carbon black, the PVDF and the solvent according to the ratio of 85:10:5, adding a proper amount of distilled water, and grinding into black slurry. The slurry was then uniformly coated on a copper foil. And (3) putting the coated copper foil into a vacuum drying oven to be dried for 5 minutes at 130 ℃, and then drying at 90 ℃ until the copper foil is completely dried.
Comparative example 2
Respectively weighing the activated carbon, the conductive carbon black, the PTFE and the solvent according to the ratio of 85:10:5, adding a proper amount of distilled water, and grinding into black slurry. The slurry was then uniformly coated on a copper foil. And (3) putting the coated copper foil into a vacuum drying oven to be dried for 5 minutes at 130 ℃, and then drying at 90 ℃ until the copper foil is completely dried.
Comparative example 3
Respectively weighing the activated carbon, the conductive carbon black, the CMC and the solvent according to the proportion of 85:10:5, adding a proper amount of distilled water, and grinding into black slurry. The slurry was then uniformly coated on a copper foil. And (3) putting the coated copper foil into a vacuum drying oven to be dried for 5 minutes at 130 ℃, and then drying at 90 ℃ until the copper foil is completely dried.
The electrode sheets prepared in example 13 and comparative examples 1 to 3 were cut, respectively, and prepared into symmetrical supercapacitors, and electrochemical tests were performed, and the results are shown in table 4.
Table 4: performance of symmetric supercapacitor made with the electrode sheets of example 13 and comparative examples 1 to 3
From electrochemical test results, compared with supercapacitors prepared by other traditional binders (PVDF, PTFE and CMC), the supercapacitors prepared by the thiophene copolymer of the invention have the advantages that the specific capacitance is improved by more than 20%, and the cycling stability is kept at more than 95% after 10000 times. And no extra solvent is needed during preparation, and the preparation process is simple and convenient.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A thiophene copolymer having the formula:
wherein, x: y is 10: 1-30: 1 and n is an integer of 1-20.
2. The thiophene copolymer of claim 1, wherein x: y is 25: 1-30: 1.
3. thiophene copolymer according to claim 1, characterized in that-CnH2n+1Is straight chain alkyl.
4. The thiophene copolymer of claim 1 or 3, wherein n is an integer from 12 to 16.
5. The preparation method of the thiophene copolymer is characterized by comprising the following steps:
providing a compound A and a compound B, wherein the structural formulas of the compound A and the compound B are as follows:
mixing a compound A and a compound B according to a molar ratio of x: y, and reacting in the presence of a solvent and a catalyst to obtain the thiophene copolymer, wherein the thiophene copolymer has a structural formula as follows:
wherein n is an integer of 1-20, x: y is 10: 1-30: 1.
6. process for the preparation of thiophene copolymers according to claim 5, wherein the molar ratio x of said compound A to said compound B: y is 25: 1-30: 1, the solvent is CHCl3The catalyst is FeCl3And the ratio of the number of moles of the catalyst to the sum of the number of moles of the compound A and the compound B is 0.5 to 1:10 to 20.
7. The method for producing a thiophene copolymer according to claim 6, wherein-C isnH2n+1Is straight chain alkyl.
8. The method for producing a thiophene copolymer according to claim 6 or 7, wherein n is an integer of 12 to 16.
9. Use of the thiophene copolymer according to any one of claims 1-4 or the thiophene copolymer prepared by the thiophene copolymer preparation method according to any one of claims 5-8 in a binder.
10. The electrode active material is characterized by comprising a thiophene copolymer, a carbon material and a curing agent, wherein the mass ratio of the thiophene copolymer to the carbon material to the curing agent is 70-95: 4.5-30: 0.01-0.5, wherein the thiophene copolymer has the following structural formula:
wherein, x: y is 10: 1-30: 1 and n is an integer of 1-20.
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| JPS58222151A (en) * | 1982-06-17 | 1983-12-23 | Matsushita Electric Ind Co Ltd | Polymer of heterocyclic five-membered ring compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS58222151A (en) * | 1982-06-17 | 1983-12-23 | Matsushita Electric Ind Co Ltd | Polymer of heterocyclic five-membered ring compound |
| CN103665348A (en) * | 2013-12-09 | 2014-03-26 | 深圳清华大学研究院 | Thiophene copolymer and preparation method thereof |
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| Substituent Effects on the Thermochemistry of Thiophenes. A Theoretical (G3(MP2)//B3LYP and G3) Study;Notario R, et al.;《The Journal of Physical Chemistry》;20120406;第116卷;第4363-4370页 * |
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